William h



provide an improved protective coating ma-.

Patented Sept. 6, 1932 i UNIT D srarss PATENT] orrlcs WILLIAM H.IVHILL, or immne'ron, NEW JERSEY, assrenon ro THE xorrnns oom- AN or DELAWARE, A ooaronarron or, DELAWARE COMPOSITIOiN orivrarrnn AND rnoonss'oi PREPARING rrnn SAME No Drawing.

This inventionrelates to compositionsof matter and processes of preparing thesame,

and more particularly to the manufacture of products containing coal.

Various bituminous products are now in common use for coating purposes, particularly for the protection of metal against corrosion or of wood against decay and for coating concrete, brick, stone surfaces,-etc. Many bituminous products have serious disadvanwhich result from thisprocedure are annoys mg to workmen and even dangerous, particularly if the work is donein closed rooms, as for instance in ships holds.

Furthermore, in most cases 1t is necessary" final coatin s often shoW a tendency to run or,

D to produce rough surfaces.

An object of the present'invention is to terial and a method of preparing the same.

In accordance with the present invention, a coal product of a plastic nature is prepared from solutionsof coal in tars and oils by the 6 addition thereto of low boilingzorganic liq- 35 and the term is herein intended to refer to a colloidally dispersed structure consisting of a solid and a liquid phase or also of two viscous'liquid phases, andhaving shape andfco-i 4 hesion, andelastic properties, although it 0 may be very rich in liquid.

i The product of this invention differs from the product described in a. copending application of H. J. Rose and V. H. Hill, Serial No. 393,124, filed Sept.v 16, 1929,. partly in that the latter product is a so-called non-- evap'orative coagulated coal solution, that is, one from which the coagulating agent evaporates very slowly or not at all, whereas the to product of the present invention is one which tages. Usually it is necessary to heat or melt them prior to application and the fumes It is also somewhat difficult to evenly Application filed September 16, 1929. Serial No. 393,115.

dries out and hardens by evaporation of the coagulating agent.

As set forth in the copending application I Serial No. 97 ,467, filed. March 25, 1926,-by

Rose" and Hill, coal maybedissolved in oils such as coal tar or water-gas tar and certain distilla'tes"therefrom; The coal and oil are brought together and heated at normal or only moderately elevated pressures and moderately elevated temperatures of from about 200 C. to about 400 C. Agiven coal is heated withthe solvent to non-decomposing temperatures, or mother words, below the temperature. at'which substantial chemical decomposition of the coal takes place.

Substantially all of. the coal dissolves, forming homogeneous. solutions which remain stable at temperatures below the point of rapid volatilization or even below the dissolvingtemperatures. The coals most easily dissolved in such'solvents are generally the coking coals. Substantially all of such coals are soluble, the insoluble portions consisting of'the mineral matteror ash and the mineral charcoal orsfus'ain which may be present in 1 limited amounts;

Preferably a high boiling coke-oven-tar oil is used as a-solvent for coal. Other oils such as cracked petroleumoils,, and especially the higher boiling distillates thereo may also be used.

A coal solution may be; prepared by heating. one part of coal, such as Pittsburgh seam coal, and about three parts of crude coke-oven tar, for instance, in a closed vesselheated directly to a temperature of about 300 C. Water and undesirable light oils are allowed to escape before the vessel isclosed. The re'sultingproduct is allowed to cool andis discharged into containers at a temperature lower than the lowest boiling temperature (about 200 C.) of compounds contained therein.

In addition to the solvents for coalmentioned above, sulphur treated oils and tars described in the co-pending application of Roseand Hill Serial No. 354,694, filed April 12, '1929, may also be used.-

In accordance with the presentprocess, a coal solution is'prepare'd by dissolving coal in any of the solvents mentioned above and the low boiling organic liquid is added to the solution formed. Practically every organic volatile solvent can be used, such as benzene, toluene, solvent naphtha, gasoline and turpentine, or, any combination of such solvents maybe added to the coal solution to produce a plastic or coagulated mass.

These low boiling organic liquids tend to thin the coal solution when added in too large amounts. The proper proportion is easily determined by the consistency obtained. In

other words, a thickened mass which is of a semi-solid, plastic, or gelatinous. nature, is.

there results a formation of 'mlnute par-- ticles of undissolved coal in the coal solvent. A given mass of treated coal solution may contain some dissolved coal and particles-of undissolved coal, or it may contain little or no dissolved coal, in wh'ich'case substantially all of the previously dissolved coal is changed to a suspensoid.

produced by any one of the following methods Y tacmnple J.One hundred pounds of coal solution having a melting pointlower than the boiling point of a volatile solvent, such as benzene, are heated to thin or liquefy the same. Then about twenty pounds of'the volatilesolvent are introduced slowly with heating and vigorous stirring or kneading until a homogeneous mass is obtained. It is advantageous to carry this out in a closed container fitted with a reflux condenser. After the resulting product is cooled, it is ready foruse; r Y

Example 2.One hundred pounds of coal solution having a meltingpoint somewhat above'the'boiling point of the volatile solvent used, forinstance about 121 C., are charged into anautoclave'having an internal stirrer, together with about thirty pounds of the volatile solvent, such as benzene. The autoclave is closed and the temperature brought up to about 200? C. While stirring the contents-ofthe autoclave. Upon cooling, the product is ready for use. r

Example 3. One hundred pounds of coal solution having a melting point somewhat above the boilingpoint ofthe volatile solvent used, for instanceabout 121 (1., are charged into a stationary autoclave, fitted.

mixture is allowed to soak for some time and is then charged into a kneading machine. As soon. as a uniform mass has been formed, an additional ten pounds of'benzene are added and the kneading continued until the mass becomes homogeneous. The total amount of solvent may be added at one time, instead of in two or more batches. The product can be used as such or it may be passed through a homogenizer or colloid mill or extrusion apparatus.

In-cases where it is desired to obtain a coating of; a higher melting point than the coal solution employed, it is advantageous to add to the volatile solvent used in preparing the coagulated product such highly coagulating agentsv as linseed oil, paratlin, etc., mentioned in the copending application of Rose and Hill, Serial No. 393,124, filed Sept. 16, 1929. Any desiredproportions of the latter agents may be used. It is preferred to add from 1% to 5% thereof with respect to the weight .of coal solution used. The same amount of volatile solvent may be used as a that given in the above examples. Upon the By way of example, coal plastics'may be.

of relatively high melting point.

Products of the preceding type are prepared in cases where conditions are such that it is impractical to prepare plastic products from high melting coal solutions.

Plastic or coagulated masses produced in accordance with the present invention may vary in consistency from a liquid to a solid, and those particularly of a soft, buttery or a'doughy consistency may be readily applied with a trowel, a putty knife or similar instrument without the use of heat. They are usually applied like-a plaster or paste in thick layers and permitted to dry out in place, producing a coating which comprises the original coal solution- After drying out, the surface of such acoating may be smoothed or sealed with. the aid of hot irons of various shapes.

Various inorganic or organic materials may be added to the coagulated coal solutions to producemasses ofvarying consistencies and to produce coatings of varying degrees of hardness. The added materials may be of a purely inert type, forexample, fillers such asbentonite clay and'sand, or pigments such as aluminum bronze and venetian red, or fibrous materials such as mineral wool, asbestos and cellulose fibres; or they may exert some chemical or physical action upon the coal solution after the evaporation of the volatile solvent, as for instance, sulphur or its compounds; or they may exert a beneficial influence upon the surface to which the plastic mass is applied, for example, corrosion inhibitors such as nitrogen bases (pyridine),

chromates, etc. Any one of or any combina tion of the above materials may be added to the coagulated coal solution in any desired proportion.

In addition to the uses mentioned above, coagulated coal solutions may be used as filling or sealing materials, or they may be used as cold patches in road construction, for roofs or other waterproofing purposes, for impregnating purposes, in molding compositions, in tree surgery, cements, binders, putties, print ers inks, etc.

It is obvious that the coal solution to be coagulated must be selected with a view to the conditions to which the final coating is to be subjected. For instance, the raw material required for the coating of surfaces which are submerged in cold water, as ships plates, differs from a material which is to be used for coating tanks which are subjected to the temperature of boiling water or for the coating of surfaces subjected to direct sun light.

In general, the coal solution should be so selected that its melting point lies well above the highest temperature to be encountered. At the same time, the temperature-susceptibility factor should be as low as possible in order to avoid brittleness when the temperature drops unusually low. This requirement is well met by coal solutions due to the fact that they have a lower susceptibility factor than the ordinary bituminous coatings.

The products of this invention are very easily applied to surfaces to be coated and they do not require primers even when they are applied to very cold surfaces. Furthermore, they produce coatings having great adhesive strength.

I claim as my invention:

1. A process of preparing bituminous products, which process comprises heating coal and oil together to non-decomposing temperatures of the coal, namely about 200 C. to 400 C., to form a homogeneous fluid benzene, toluene, solvent naphtha, gasoline and turpentine, in suflicient amount only to increase the consistency of the said fluid mass.

3. A bituminous product comprising coal and oil which have been heated together to non-decomposing temperatures of about 200 C. to 400 C. to form a homogeneous fluid mass of coal and oil, and a volatile solvent selected from a group consisting of benzene, toluene, solvent naphtha, gasoline, and turpentine in. sufficient amount to form a thickened soft mass. I

4:. A bituminous product consisting of a thickenedsoft mass comprising a previously dissolved coal uniformly distributed in a solvent for the coal, and benzene in an amount insuflicient to cause settling of the coal.

5. A process of preparing bituminous products, which process comprises heating coal and oil together to non-decomposing temperatures of the coal, namely about 200 C. to 400 C. to form a homogeneous fluid mass of coal and oil and thickening the said fluid mass by adding a volatile solvent which if added in a relatively small amount will increase the consistency of the said fluid mass but if added in large amounts will thin the said fluid mass.

In testomony whereof, I have hereunto subscribed my name this 9th day of September, 1929. p WILLIAM H. HILL.

mass of coal and oil, maintaining the said mass in a fluid state, and mixing with the said mass a volatile solvent containing at least one of a group consisting of benzene, toluene, solvent naphtha, gasoline and turpentine, in sufficient amount only to thicken the said fluid mass.

2. A process of preparing bituminous products, which process comprises heating coal and oil together in the form of a homogeneous fluid mass at a temperature below the temperature at which chemical decomposition of the coal takesplace and mixing with the said fluid mass a volatlle solvent contalnlng at least one of a group consisting of 

